CN116514568A - Ceramic-metal integrated package and packaging method - Google Patents
Ceramic-metal integrated package and packaging method Download PDFInfo
- Publication number
- CN116514568A CN116514568A CN202310347000.8A CN202310347000A CN116514568A CN 116514568 A CN116514568 A CN 116514568A CN 202310347000 A CN202310347000 A CN 202310347000A CN 116514568 A CN116514568 A CN 116514568A
- Authority
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- China
- Prior art keywords
- powder
- ceramic
- molybdenum
- manganese
- nickel
- Prior art date
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- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 143
- 239000002184 metal Substances 0.000 title claims abstract description 143
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 148
- 239000000919 ceramic Substances 0.000 claims abstract description 132
- 229910000679 solder Inorganic materials 0.000 claims abstract description 120
- 239000011230 binding agent Substances 0.000 claims abstract description 105
- 239000000843 powder Substances 0.000 claims abstract description 75
- 239000000178 monomer Substances 0.000 claims abstract description 74
- PCEXQRKSUSSDFT-UHFFFAOYSA-N [Mn].[Mo] Chemical compound [Mn].[Mo] PCEXQRKSUSSDFT-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 60
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 238000003466 welding Methods 0.000 claims abstract description 26
- 239000000853 adhesive Substances 0.000 claims abstract description 20
- 230000001070 adhesive effect Effects 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims description 59
- 238000001465 metallisation Methods 0.000 claims description 35
- 238000000576 coating method Methods 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 25
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229910052573 porcelain Inorganic materials 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 238000007650 screen-printing Methods 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 18
- 239000010410 layer Substances 0.000 description 102
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 14
- 238000001878 scanning electron micrograph Methods 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 11
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 229940116411 terpineol Drugs 0.000 description 11
- 239000008346 aqueous phase Substances 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 230000001052 transient effect Effects 0.000 description 7
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical group CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- -1 N-methacrylamide Chemical compound 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 238000007665 sagging Methods 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 238000005476 soldering Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000005251 gamma ray Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 238000004021 metal welding Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- YRVUCYWJQFRCOB-UHFFFAOYSA-N n-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009323 psychological health Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
- C04B37/023—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
- C04B37/028—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles by means of an interlayer consisting of an organic adhesive, e.g. phenol resin or pitch
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Products (AREA)
Abstract
The invention discloses a ceramic-metal integrated package and a packaging method. The thickness of the molybdenum-manganese layer is 5-30 microns, and the molybdenum-manganese layer comprises the following raw material components: ceramic metal powder and binder solution; the thickness of the nickel metal layer is 0.5-15 micrometers, and the nickel metal layer comprises the following raw material components: nickel powder and binder solution; the thickness of the solder layer is 3-100 micrometers, and the solder layer comprises the following raw material components: solder powder and a binder solution. The binder solution comprises a binder and water, wherein the mass ratio of the binder to the water is (0.2-1.5): 1; the adhesive is a polymer with a hydrophilic monomer and a hydrophobic monomer, and the mass ratio of the hydrophilic monomer to the hydrophobic monomer is 1: (0.15-18). The invention simplifies the welding assembly process, is environment-friendly and has higher welding reliability.
Description
Technical Field
The invention relates to the technical field of ceramic packaging, in particular to a ceramic-metal integrated packaging piece and a packaging method.
Background
The excellent properties of ceramics and metals can be fully exerted only after the ceramics and the metals are firmly connected, but the ceramics are difficult to be directly combined with the metals due to the fact that the atomic structures of the ceramics and the metals are different and the physical and chemical properties are not matched. At present, a molybdenum-manganese metal layer and a nickel metal layer are coated on the surface of ceramic in sequence to metalize the ceramic, and then the ceramic is welded with metal to be welded, wherein the molybdenum-manganese metal layer is prepared by dispersing molybdenum powder and manganese powder into a glue solution which uses ethyl cellulose as a binder and terpineol as a solvent to prepare slurry, screen-printing the slurry on the surface of the ceramic, and then treating the slurry in a hydrogen furnace at high temperature after drying. The nickel metal layer has the main functions of enhancing the fluidity of the solder, isolating the molybdenum-manganese layer from the solder and preventing the solder from corroding the molybdenum-manganese metallized layer to influence the welding strength and the air tightness. The nickel metal layer is generally formed by electroplating, and a thinner and compact nickel metal layer is deposited in the molybdenum-manganese metallized ceramic electroplating solution. The welding is generally carried out by using a special stainless steel or graphite welding die, stacking the metal piece to be welded, the noble metal solder piece and the ceramic matrix, and then placing the stacked metal piece, the noble metal solder piece and the ceramic matrix in an inert atmosphere furnace for welding.
The prior art process mainly has the following problems: 1. the special smell of terpineol seriously affects the physical and psychological health of production workers; 2. the use of terpineol in large amounts increases the production cost of the slurry; 3. because terpineol is thicker, the slurry preparation and printing process are often carried out at a temperature of more than 50 ℃ so as to ensure that the slurry can be leveled on the ceramic surface; 4. electroplating wastewater generated during electroplating can cause serious environmental pollution; 5. because the noble metal solder chip contains some brittle phases, the plasticity is poor, the solder chip is thicker, a large amount of noble metal is left in the ceramic-metal space, and the waste is serious.
Disclosure of Invention
The invention provides a ceramic-metal integrated package and a packaging method thereof, which are used for solving the technical problems of complex welding assembly process, environmental protection and lower welding reliability.
According to one aspect of the invention, there is provided a ceramic-metal integrated package comprising a ceramic body, a molybdenum-manganese layer, a nickel metal layer, a solder layer and a metal piece connected in sequence, wherein the thickness of the molybdenum-manganese layer is 5-30 microns, and the ceramic-metal integrated package comprises the following raw material components: the ceramic metal powder and the binder solution are mixed according to the mass ratio of (0.5-3): 1, wherein the ceramic metal powder comprises the following components in parts by weight: 60-86 parts of molybdenum powder, 7-20 parts of manganese powder and 7-20 parts of porcelain powder;
The thickness of the nickel metal layer is 0.5-15 micrometers, and the nickel metal layer comprises the following raw material components: the nickel powder and the binder solution are in a mass ratio of (1-3): 1, a step of;
the thickness of the solder layer is 3-100 micrometers, and the solder layer comprises the following raw material components: the solder powder and the binder solution, wherein the mass ratio of the solder powder to the binder solution is (0.5-2): 1, a step of; wherein the solder powder comprises at least two of silver powder, zinc powder, copper powder, manganese powder, chromium powder, iron powder, cobalt powder, titanium powder, nickel powder, molybdenum powder or tin powder;
the binder solution comprises a binder and water, wherein the mass ratio of the binder to the water is (0.2-1.5): 1; the adhesive is a polymer with a hydrophilic monomer and a hydrophobic monomer, and the mass ratio of the hydrophilic monomer to the hydrophobic monomer is 1: (0.15-18);
the structural formula of the hydrophobic monomer is CH 2 ＝CR 1 R 2 Wherein R is 1 is-H or-CH 3 ；R 2 is-CN, -C 6 H 5 、-COOR 3 Wherein R is 3 Is alkyl, cycloalkyl or aryl;
the structural formula of the hydrophilic monomer is as follows: CHR (CHR) 4 ＝CR 5 R 6 Wherein R is 4 And R is 5 Are all-H or-CH 3 or-COOM; r is R 6 is-COOM, -CH 2 COOM、-COO(CH 2 ) 6 SO 3 M、-CONH 2 、-CONHR 7 Wherein R is 7 Is alkyl or cycloalkyl; m is any one of H element or metal element related in ceramic metal powder.
Further, the composition of the ceramic powder is consistent with or close to the composition of the ceramic body.
Further, in the molybdenum-manganese layer, the particle size of the molybdenum powder and the manganese powder is less than or equal to 10 micrometers.
Further, in the nickel metal layer, the nickel powder particle size is less than or equal to 5 microns.
Further, in the solder layer, the particle size of the solder powder is less than or equal to 50 micrometers.
According to another aspect of the present invention, there is also provided a packaging method of the above ceramic-metal integrated package, including the steps of:
(1) Molybdenum-manganese metallization: mixing molybdenum powder, manganese powder and porcelain powder, adding a binder solution, and stirring at 1-90 ℃ to obtain ceramic molybdenum-manganese metallized slurry; coating the obtained ceramic molybdenum-manganese metallized slurry on the surface of a ceramic body, and then drying and sintering to obtain a molybdenum-manganese metallized ceramic piece;
(2) Nickel metallization: stirring and mixing nickel powder and binder solution at 1-90 ℃ to obtain nickel metallization slurry; coating the obtained nickel-metallized slurry on the surface of the molybdenum-manganese metallized ceramic piece, and then drying and sintering to obtain the nickel-metallized ceramic piece;
(3) Pre-coating a solder layer: stirring and mixing the solder powder and the binder solution at the temperature of 1-90 ℃ to obtain solder paste; coating the obtained solder paste on the surface of a nickel-metallized ceramic piece, and then drying and sintering to obtain a ceramic piece pre-coated with a solder layer;
(4) Packaging a metal piece: and welding the metal piece and the ceramic piece with the obtained pre-coated welding layer to obtain the ceramic-metal integrated package piece.
Further, in the steps (1) to (3), the coating mode includes screen printing, spot coating, spray coating, roll coating, dip coating or sputtering.
Further, the viscosity of the ceramic molybdenum manganese metalized slurry in the step (1) is 1500-6000 mPa.s.
Further, the viscosity of the nickel metallization paste in the step (2) is 2500-4000 mPa.s.
Further, the viscosity of the solder paste in the step (3) is 3500-5500 mPa.s.
The invention has the following beneficial effects:
(1) The ceramic-metal integrated packaging piece and the packaging method provided by the invention simplify the subsequent welding assembly process, can improve the production efficiency by more than 2 times, and greatly improve the product yield.
Taking ceramic discharge tube products as an example, the whole assembly time takes about 10 minutes by adopting the existing welding and packaging technology. Because the thickness of the silver-copper solder sheet is about 100 micrometers, the silver-copper solder sheet is extremely thin, and when the silver-copper solder sheet is filled, dislocation, warping and the like are easy to occur, so that the yield of the product is lower than 90 percent, and in addition, for this reason, the assembly time is mainly concentrated on the arrangement and filling of the solder sheet. The process flow for solder packaging ceramic discharge tube products using prior art methods is shown in fig. 1.
According to the ceramic-metal integrated package and the packaging method, the extremely thin silver-copper solder sheets are not required to be arranged and filled, the whole assembly time only needs to take about 5 minutes, the problem that the solder sheets are easy to misplace, bend, warp and the like to cause low product yield is avoided, and the yield can reach more than 99%. The process flow of solder packaging ceramic discharge tube products using the method of the present invention is shown in fig. 2.
(2) The preparation process of the slurry only uses water as a solvent, the water is colorless and odorless, the physical and mental health of production workers cannot be damaged in the drying process, the environment is protected, and the solvent cost is reduced.
(3) The invention prepares the sizing agent and the printing sizing agent at normal temperature, thereby reducing the energy consumption cost.
(4) The invention uses the solder paste to replace the noble metal solder sheet, thereby saving the consumption of noble metals such as silver, copper and the like by more than 50 percent and reducing the cost of raw materials.
(5) The improvement of the slurry stability enables the thickness deviation of the metal layer to be less than 2%, and thoroughly solves the problem of low welding reliability caused by the grooves, such as cold joint, weak strength and the like.
In conclusion, the invention is a novel ceramic and metal welding technology with environmental protection, simple process, low cost and high welding reliability.
In addition to the objects, features and advantages described above, the present invention has other objects, features and advantages. The present invention will be described in further detail with reference to the drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a process flow diagram of a solder package for ceramic discharge tube products using prior art methods;
FIG. 2 is a process flow diagram of a solder package for ceramic discharge tube products using the method of the present invention;
FIG. 3 is a topography of a molybdenum manganese metal layer of example 1 of the present invention;
FIG. 4 is a topography of the nickel metal layer of example 1 of the present invention;
FIG. 5 is a topography of the pre-coated solder layer of example 1 of the present invention;
FIG. 6 is a diagram showing the morphology of a ceramic seal ring for a power lithium ion battery in example 2 of the present invention;
FIG. 7 is a cross-sectional SEM image of comparative example 1 of the present invention;
FIG. 8 is a graph showing the tensile strength of comparative example 1 and example 2 according to the present invention;
FIG. 9 is a topography of a 5G ceramic transient diode of example 3 of the invention;
FIG. 10 is a cross-sectional SEM image of comparative example 2 of the present invention;
FIG. 11 is a graph showing the tensile strength of comparative example 2 and example 3 according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the present invention will be further described in detail with reference to examples. It should be understood that the examples described in this specification are for the purpose of illustrating the invention only and are not intended to limit the invention.
For simplicity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
In the description herein, unless otherwise indicated, "above" and "below" are intended to include the present number, "one or more" means two or more, and "one or more" means two or more.
The embodiment of the first aspect of the invention provides a ceramic-metal integrated package, which comprises a ceramic body, a molybdenum-manganese layer, a nickel metal layer, a solder layer and a metal piece which are sequentially connected, wherein the thickness of the molybdenum-manganese layer is 5-30 micrometers, and the ceramic-metal integrated package comprises the following raw material components: the ceramic metal powder and the binder solution are mixed according to the mass ratio of (0.5-3): 1, wherein the ceramic metal powder comprises the following components in parts by weight: 60-86 parts of molybdenum powder, 7-20 parts of manganese powder and 7-20 parts of porcelain powder;
the thickness of the nickel metal layer is 0.5-15 micrometers, and the nickel metal layer comprises the following raw material components: the nickel powder and the binder solution are in a mass ratio of (1-3): 1, a step of;
the thickness of the solder layer is 3-100 micrometers, and the solder layer comprises the following raw material components: the solder powder and the binder solution, wherein the mass ratio of the solder powder to the binder solution is (0.5-2): 1, a step of; wherein the solder powder comprises at least two of silver powder, zinc powder, copper powder, manganese powder, chromium powder, iron powder, cobalt powder, titanium powder, nickel powder, molybdenum powder or tin powder;
the binder solution comprises a binder and water, wherein the mass ratio of the binder to the water is (0.2-1.5): 1; the adhesive is a polymer with a hydrophilic monomer and a hydrophobic monomer, and the mass ratio of the hydrophilic monomer to the hydrophobic monomer is 1: (0.15-18);
The structural formula of the hydrophobic monomer is CH 2 ＝CR 1 R 2 Wherein R is 1 is-H or-CH 3 ；R 2 is-CN, -C 6 H 5 、-COOR 3 Wherein R is 3 Is alkyl, cycloalkyl or aryl;
the structural formula of the hydrophilic monomer is as follows: CHR (CHR) 4 ＝CR 5 R 6 Wherein R is 4 And R is 5 Are all-H or-CH 3 or-COOM; r is R 6 is-COOM, -CH 2 COOM、-COO(CH 2 ) 6 SO 3 M、-CONH 2 、-CONHR 7 Wherein R is 7 Is alkyl or cycloalkyl; m is any one of H element or metal element related in ceramic metal powder.
In the embodiment of the invention, the thickness of the molybdenum-manganese layer is 5-30 microns, and the molybdenum-manganese layer comprises the following raw material components: the ceramic metal powder and the binder solution are mixed according to the mass ratio of (0.5-3): 1, for example, the mass ratio of the ceramic metal powder to the binder solution is 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, or 3:1, etc., and the mass ratio of the ceramic metal powder to the binder solution may also be any combination range of the above values.
Wherein, the ceramic metal powder comprises the following components in parts by weight: 60-86 parts of molybdenum powder, 7-20 parts of manganese powder and 7-20 parts of porcelain powder; in some embodiments, the molybdenum powder may be 60 parts, 64 parts, 68 parts, 70 parts, 75 parts, 80 parts, 86 parts, or the like, and the molybdenum powder may also be in any combination of the above values. In some embodiments, the manganese powder may be 7 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, etc., and the mass parts of the manganese powder may also be any combination of the above values. In some embodiments, the ceramic powder may be 7 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, etc., and the mass parts of the ceramic powder may also be any combination of the above values.
In the embodiment of the invention, the thickness of the nickel metal layer is 0.5-15 microns, and the nickel metal layer comprises the following raw material components: the nickel powder and the binder solution are in a mass ratio of (1-3): 1, a step of; for example, the mass ratio of nickel powder to binder solution is 1:1, 1.5:1, 2:1, 2.5:1, or 3:1, etc., which may also be any combination of the above values.
In the embodiment of the invention, the thickness of the solder layer is 3-100 micrometers, and the solder layer comprises the following raw material components: the solder powder and the binder solution, wherein the mass ratio of the solder powder to the binder solution is (0.5-2): 1, a step of; for example, the mass ratio of solder powder to binder solution is 0.5:1, 1:1, 1.5:1, 2:1, etc., which may also be any combination of the above values.
Wherein the solder powder comprises at least two of silver powder, zinc powder, aluminum powder, copper powder, manganese powder, chromium powder, iron powder, cobalt powder, titanium powder, nickel powder, molybdenum powder or tin powder, for example, a combination of silver powder and zinc powder, or a combination of silver powder, copper powder and manganese powder, or a combination of iron powder and cobalt powder, or a component of chromium powder, iron powder and nickel powder, etc.
In an embodiment of the present invention, the binder solution includes a binder and water in a mass ratio of (0.2-1.5): 1, for example, the mass ratio of the binder to water is 0.2:1, 0.5:1, 0.8:1, 1:1, 1.2:1, or 1.5:1, etc., and the mass ratio of the binder to water may also be any combination range of the above values.
In an embodiment of the present invention, the binder is a polymer with both hydrophilic and hydrophobic monomers, and the mass ratio of the hydrophilic monomer to the hydrophobic monomer is 1: (0.15-18), for example, the mass ratio of hydrophilic monomer to hydrophobic monomer is 1:0.15, 1:0.5, 1: 1. 1: 2. 1: 5. 1: 8. 1:10, 1:12, 1:15, 1:18, etc., the mass ratio of hydrophilic monomer to hydrophobic monomer may also be in any combination of the above values. The binder can play a role in dispersing the surfactant, on one hand, the hydrophilic group of the binder interacts with the ceramic metal powder, and on the other hand, the hydrophobic group of the binder utilizes the hydrophobicity of the binder to prevent aggregation and sedimentation of materials. Therefore, when the mass ratio of the hydrophilic monomer to the hydrophobic monomer is too large or too small, the dispersibility thereof cannot be effectively exerted, resulting in unstable slurry and easy sedimentation.
In an embodiment of the invention, the binder is a polymer with both hydrophilic and hydrophobic monomers, the hydrophilic monomers including one or more of acrylic acid, acrylic acid salts, acrylamides (acrylamide, N-methacrylamide, N-ethylacrylamide, N-butylacrylamide, 2-methacrylamide), vinylsulfonic acid salts, methacrylic acid salts, acrylic acid, acrylic sulfonic acid salts, 2-acrylamido-2-methylpropanesulfonic acid, itaconic acid salts, and maleic acid. The hydrophobic monomer comprises one or more of cyclohexyl acrylate, acrylonitrile, styrene, acrylic acid esters (methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, octyl acrylate, vinyl acetate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, epoxypropyl methacrylate and the like), methacrylonitrile.
In some embodiments, the binder comprises acrylic acid (hydrophilic monomer) and vinyl acetate (hydrophobic monomer), and the method of making comprises: 18 parts by mass of acrylic acid and distilled water are added into a reaction kettle, dissolved under high-speed stirring, 12 parts by mass of vinyl acetate are added, an initiator is added to initiate a reaction at 60 ℃, and stirring is continued until the reaction is completed, so that the water-based adhesive is obtained.
In other embodiments, the binder comprises acrylamide (hydrophilic monomer) and butyl acrylate (hydrophobic monomer), specifically prepared: adding 40 parts by mass of acrylamide and distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min; introducing nitrogen; heating to 70 ℃, and then adding 60 parts by mass of butyl acrylate to the temperature which is constant at 70 ℃; then adding initiator ammonium persulfate to initiate reaction, taking out precipitate after reacting for 9 hours, adding ammonia water to neutralize pH to 6.5-9, and obtaining the aqueous adhesive.
In order to obtain the desired adhesion, the adhesive must be well wetted with the adherend. According to the young's wetting equation:
γ s ＝γ sl +γ sl cos θ (1.1)
A kind of electronic device with high-pressure air-conditioning system
W sl ＝γ s +γ l -γ sl (1.2)
Substituting formula 1.2 into 1.1 to obtain
W sl ＝γ l (1+cos θ) (1.3)
Wherein: w (W) sl -adhesion between solid and liquid; gamma ray l -liquid surface tension in a solid medium; gamma ray s -solid surface tension in gaseous medium; gamma ray sl -surface tension of the solid in contact with the liquid; θ—contact angle between solid and liquid.
As can be seen from equation 1.3, the adhesion between the adhesive and the adherend is mainly affected by both the surface tension and the contact angle. On the other hand, if θ<90 °, i.e. as the angle becomes smaller, the liquid wets the solid more easily; if theta is>The liquid is spherical at 90 degrees, cannot wet the solid, and is easy to move on the surface of the solid. When θ=0, the adhesion force may take a maximum value. In actual life, however, θ cannot be 0 °, and therefore the contact angle is made as small as possible. On the other hand, as can be seen from formula 1.1, when θ is as small as possible, γ s ＝γ l +γ sl Small, negligible, i.e., good wetting when the surface tension of the liquid is consistent with the surface tension of the solid.
In the ceramic-metal integrated packaging piece provided by the invention, the thickness of the molybdenum-manganese layer is 5-30 microns, the raw material components comprise ceramic metal powder and binder solution, the surface tension of a slurry system prepared by the binder mainly depends on an aqueous solvent, as the viscosity of water is much smaller than that of terpineol, that is, the interaction between water molecules is smaller than that of terpineol, the surface tension of the slurry system can be reduced by using water as a solvent, so that the surface tension of the slurry system is close to that of a ceramic matrix, and the use of the binder in the molybdenum-manganese layer can avoid grooves with thick sides and thin middle parts due to overlarge surface tension of the slurry. Meanwhile, a large number of functional groups such as carboxyl, hydroxyl and the like in the adhesive molecules and powder materials such as molybdenum, manganese and the like and surface components of a ceramic matrix can form stronger physical and chemical acting forces in the modes of adsorption, mutual diffusion, electrostatic action and the like, so that a better gluing effect is realized.
The relative average deviation of the thickness of the whole molybdenum-manganese metal layer is less than 2 percent, and no groove exists in the prior art. Compared with the prior art, the thickness of the molybdenum-manganese metallized layer is generally 10-30 microns, the relative average deviation of the thickness of the whole metal layer is more than 30 percent, the consumption of the molybdenum-manganese can be saved by more than 50 percent, a good flatness condition is provided for nickel coating by adopting a nickel sintering process, silver-copper solder is not required to fill the groove, the consumption of silver-copper noble metal can be saved by more than 50 percent, and the expansion of the thinner molybdenum-manganese layer at high temperature can be reduced, and the welding strength can be increased.
In the ceramic-metal integrated packaging piece provided by the invention, the raw materials of the nickel metal layer comprise nickel powder and binder solution, the surface tension of a slurry system prepared from an aqueous binder mainly depends on an aqueous solvent, and as the viscosity of water is much smaller than that of terpineol, that is, the interaction between water molecules is smaller than that of terpineol, the surface tension of the slurry system can be reduced by using water as a solvent, so that the surface tension of the slurry system is close to that of a molybdenum-manganese metal layer, and surface roughness caused by overlarge surface tension of the slurry is avoided. Meanwhile, a large number of functional groups such as carboxyl, hydroxyl and the like in the adhesive molecules and the surface components of the nickel powder material and the molybdenum-manganese metal layer can form stronger physical and chemical acting forces in the modes of adsorption, mutual diffusion, electrostatic action and the like, so that a better gluing effect is realized.
In the ceramic-metal integrated packaging part provided by the invention, the raw materials of the solder layer comprise solder powder and binder solution, the surface tension of a slurry system prepared from the aqueous binder mainly depends on an aqueous solvent, and as the viscosity of water is much smaller than that of terpineol, that is, the interaction between water molecules is smaller than that of terpineol, the surface tension of the slurry system can be reduced by using water as a solvent, so that the surface tension of the slurry system is close to that of a nickel metal layer, and surface roughness caused by overlarge surface tension of the slurry is avoided. Meanwhile, a large number of carboxyl, hydroxyl and other functional groups in the adhesive molecules and the surface components of the silver-copper solder powder and the nickel metal layer can form stronger physical and chemical acting forces in the modes of adsorption, mutual diffusion, electrostatic action and the like, so that a better gluing effect is realized.
In an embodiment of the invention, the composition of the porcelain powder is consistent with or near the composition of the ceramic body. The porcelain powder is predominantly a mixture that is consistent with or close to the ceramic body composition during the metallization process, and in some embodiments, the porcelain powder includes Al 2 O 3 、SiO 2 CaO, mgO and MnO 2 One or more combinations thereof. The ceramic powder can form glass phase to fill the gaps of the molybdenum-manganese metal layer at high temperature, and has excellent compatibility due to the consistency of the glass phase and the ceramic body, so that the bonding force and compactness between the molybdenum-manganese metal layer and the ceramic body are improved.
In an embodiment of the present invention, in the molybdenum-manganese layer, the particle size of the molybdenum powder and the manganese powder is less than or equal to 10 micrometers. When the particle size of the molybdenum powder and the manganese powder is higher than 10 microns, the quality is heavy, the stability of the slurry is poor, and sedimentation is easy to occur.
In an embodiment of the present invention, in the nickel metal layer, the nickel powder has a particle size of less than or equal to 5 μm. When the particle size of the nickel powder is higher than 5 microns, the quality is heavy, the stability of the slurry is poor, sedimentation is easy to occur, the thickness of the nickel layer is thinner than 0.5-15 microns, and therefore, the particle size of the nickel powder cannot be higher than 5 microns. For example, the nickel powder particle size is 5 microns, 4 microns, 3 microns, 2 microns or less than 2 microns.
In an embodiment of the present invention, in the solder layer, a solder powder particle size is less than or equal to 50 micrometers. Considering that the thickness of the solder layer is 3-100 microns, the density of the solder is larger, and when the particle size of the solder powder is higher than 50 microns, the quality is heavy, the stability of the slurry is poor, and sedimentation easily occurs. For example, the solder powder particle size is 50 microns, 40 microns, 30 microns, 20 microns, 10 microns, or less than 10 microns.
An embodiment of the second aspect of the present invention provides a packaging method of the above ceramic-metal integrated package, including the following steps: (1) molybdenum manganese metallization: mixing molybdenum powder, manganese powder and porcelain powder, adding a binder solution, and stirring at 1-90 ℃ to obtain ceramic molybdenum-manganese metallized slurry; coating the obtained ceramic molybdenum-manganese metallized slurry on the surface of a ceramic body, and then drying and sintering to obtain a molybdenum-manganese metallized ceramic piece;
(2) Nickel metallization: stirring and mixing nickel powder and binder solution at 1-90 ℃ to obtain nickel metallization slurry; coating the obtained nickel-metallized slurry on the surface of the molybdenum-manganese metallized ceramic piece, and then drying and sintering to obtain the nickel-metallized ceramic piece;
(3) Pre-coating a solder layer: stirring and mixing the solder powder and the binder solution at the temperature of 1-90 ℃ to obtain solder paste; coating the obtained solder paste on the surface of a nickel-metallized ceramic piece, and then drying and sintering to obtain a ceramic piece pre-coated with a solder layer;
(4) Packaging a metal piece: and welding the metal piece and the ceramic piece with the obtained pre-coated welding layer to obtain the ceramic-metal integrated package piece.
The packaging method of the ceramic-metal integrated packaging part provided by the invention can be carried out at normal temperature or high temperature in the configuration process of ceramic metallization slurry, nickel metallization slurry and welding slurry, such as stirring and mixing at 1 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ and 90 ℃. Particularly, the stirring at normal temperature does not need to heat the material, so that the cost is saved, the environment is protected, and the health of operators is not affected.
In an embodiment of the present invention, in step (1) to step (3), the coating manner includes printing by screen, spot coating, spray coating, roll coating, dip coating or sputtering; the three slurries in the steps (1) to (3) can be coated at the temperature of 5-60 ℃, specific requirements on the production environment are not needed, the energy consumption and the cost are reduced, and the consistency of products is improved.
In an embodiment of the present invention, the viscosity of the ceramic molybdenum manganese metallization paste in the step (1) is 1500-6000mpa·s. When the viscosity of the ceramic metalized slurry is lower than 1500 mPa.s, the slurry is easy to settle and easy to overflow during coating; when the viscosity is higher than 6000 mPa.s, the fluidity of the slurry becomes poor, the slurry cannot be scraped, and the coating is easy to crack.
In an embodiment of the invention, the viscosity of the nickel metallization paste in step (2) is 2500-4000 mPa-s.
Sagging of nickel paste at different temperatures: the slurry is in a fine string shape when sagging at 60 ℃, which indicates that the slurry has good sagging degree. When the temperature is reduced to 40 ℃ and even 5 ℃, the slurry still presents a tiny string shape when sagging, which indicates that the sagging degree of the slurry is less affected by the temperature. The viscosity of the nickel slurry changes with temperature: the viscosity of the paste at 60 ℃ is about 2500 mPa-s, the viscosity starts to rise slowly with decreasing temperature, and when the temperature is decreased to 5 ℃, the viscosity of the paste rises to about 4000 mPa-s, and the viscosity of the paste is not greatly changed as a whole, and the paste is suitable for the subsequent printing process.
In an embodiment of the present invention, the viscosity of the solder paste in the step (3) is 3500-5500mpa·s.
Taking AgCu28 solder paste as an example, the viscosity changes with temperature: the viscosity of the paste at 60 ℃ is about 3500 mPa-s, the viscosity starts to rise slowly with decreasing temperature, and when the temperature is decreased to 5 ℃, the viscosity of the paste rises to about 5500 mPa-s, and the viscosity of the paste is not greatly changed as a whole, and is suitable for the subsequent printing process.
In an embodiment of the invention, the drying temperature after application of the three slurries of steps (1) to (3) is 40-110 ℃, preferably 60 ℃.
In an embodiment of the invention, the sintering temperature of the molybdenum manganese metallization in step (1) is 1480-1580 ℃, preferably 1500 ℃; the holding time is 60 to 90min, preferably 75min.
In an embodiment of the invention, the sintering temperature of the nickel metallization in step (2) is 900-1100 ℃, preferably 1000 ℃; the holding time is 60 to 90min, preferably 75min.
In an embodiment of the present invention, the sintering temperature of the pre-coated solder layer in step (3) is 600-900 ℃, preferably 800 ℃; the holding time is 5 to 60min, preferably 20min.
Examples
The following examples more particularly describe the disclosure of the present application, which are intended as illustrative only, since numerous modifications and variations within the scope of the disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1
The embodiment provides a ceramic-metal integrated package, and the preparation method comprises the following steps:
(1) Molybdenum-manganese metallization: mixing molybdenum powder, manganese powder and porcelain powder, adding a binder solution, and stirring at normal temperature to obtain ceramic metallization slurry; the viscosity of the ceramic metallization slurry is about 2460 mPa.s at normal temperature. And (3) at normal temperature, coating the obtained ceramic metalized slurry on the surface of a ceramic piece in a screen printing mode, wherein a screen is 200 meshes, and then drying and sintering to obtain the metalized ceramic piece. Wherein the drying temperature is 60 ℃ and the drying time is 40 minutes. The sintering temperature is 1500 ℃, and the heat preservation time is 75 minutes. The ceramic piece is a ceramic ring with the diameter of 8mm, the wall thickness of 0.8mm and the height of 10mm, and the molybdenum-manganese metallization is processed on the end face of the ceramic ring.
The raw material components for the molybdenum-manganese metallization comprise: the ceramic metal powder comprises the following components in parts by weight: 70 parts of molybdenum powder; 15 parts of manganese powder; 15 parts of porcelain powder; the binder solution comprises a binder and water, wherein the mass ratio of the binder to the water is 1:1, and the mass ratio of hydrophilic monomers to hydrophobic monomers in the binder is 1:18, wherein the hydrophobic monomer is acrylonitrile, the hydrophilic monomer is acrylic acid salt, and the acrylic acid nitrile and acrylic acid salt are copolymerized in an aqueous phase to prepare the adhesive.
Fig. 3 (a) is a surface view of the dried molybdenum-manganese metal layer, and it can be seen from fig. 1 that the surface of the molybdenum-manganese metal layer is uniform and flat.
FIGS. 3 (b) and 3 (c) are Scanning Electron Microscope (SEM) images of the molybdenum-manganese metallized ceramic member, and FIG. 3 (b) is a front SEM image of the molybdenum-manganese metal layer, which shows that the surface is flat and uniform without grooves; fig. 3 (c) is a cross-sectional SEM image of the molybdenum-manganese metal layer, showing that the surface layer is relatively uniform in thickness, on the order of about 10 microns.
(2) Nickel metallization: stirring and mixing nickel powder and a binder solution at normal temperature to obtain nickel metallization slurry; the viscosity of the nickel metallization paste is about 3250 mPa.s at normal temperature. And at normal temperature, coating the obtained nickel-metallized slurry on the surface of the molybdenum-manganese metallized ceramic piece in a screen printing mode, and then drying and sintering to obtain the nickel-metallized ceramic piece. Wherein the drying temperature is 60 ℃ and the drying time is 40 minutes. The sintering temperature is 1000 ℃ and the heat preservation time is 75 minutes.
The raw material components for nickel metallization comprise: nickel powder and binder solution, wherein the mass ratio of the nickel powder to the binder solution is 1.5:1, wherein the mass ratio of the binder to the water is 1:1, and the mass ratio of the hydrophilic monomer to the hydrophobic monomer in the binder is 1:18, wherein the hydrophobic monomer is acrylonitrile, the hydrophilic monomer is acrylic acid salt, and the acrylic acid nitrile and acrylic acid salt are copolymerized in an aqueous phase to prepare the adhesive.
Fig. 4 (a) is a surface view of the nickel metal layer after being dried, and it can be seen that the nickel metal layer has a uniform and flat surface.
FIGS. 4 (b) and 4 (c) are Scanning Electron Microscope (SEM) images of a nickel-metallized ceramic article, and FIG. 4 (b) is a front SEM image of a nickel metal layer, which shows that the surface is flat and uniform, and no grooves are seen; fig. 4 (c) is a cross-sectional SEM image of the nickel metal layer, showing that the surface layer is relatively uniform in thickness, about 10 μm.
(3) Pre-coating a solder layer: and stirring and mixing the solder powder and the binder solution at normal temperature to obtain solder paste, wherein the viscosity of the solder paste at normal temperature is about 4160 mPa.s. And (3) at normal temperature, coating the obtained solder paste on the surface of the nickel-metallized ceramic piece, and then drying and sintering to obtain the ceramic piece pre-coated with the solder layer. Wherein the drying temperature is 60 ℃ and the drying time is 40 minutes. The sintering temperature is 800 ℃, the heat preservation time is 20 minutes, and the sintering atmosphere is hydrogen or inert atmosphere.
The raw material components used for the precoating solder layer comprise: a solder powder and a binder solution, wherein the mass ratio of the solder powder to the binder solution is 1.5:1, wherein the solder powder is a mixture of copper powder and silver powder, the mass ratio of the binder to water is 1:1, and the mass ratio of hydrophilic monomer to hydrophobic monomer in the binder is 1:18, wherein the hydrophobic monomer is acrylonitrile, the hydrophilic monomer is acrylic acid salt, and the acrylic acid nitrile and acrylic acid salt are copolymerized in an aqueous phase to prepare the adhesive.
FIGS. 5 (a) and 5 (b) are Scanning Electron Microscope (SEM) images of a ceramic part pre-coated with a solder layer, and FIG. 5 (a) is a front SEM image of a pre-coated solder layer, which shows that the surface is flat and uniform and no grooves are seen; fig. 5 (b) is a cross-sectional SEM image of the pre-coated solder layer, showing that the surface layer is relatively uniform in thickness, on the order of 5 microns.
(4) Packaging a metal piece: and (3) loading the metal piece to be welded and the ceramic piece pre-coated with the welding layer, and welding in a vacuum furnace, a reducing atmosphere furnace or an inert atmosphere furnace to realize the encapsulation of the ceramic end face and the metal piece, thereby obtaining the encapsulated ceramic.
Example 2
Taking a ceramic sealing ring product for a power type lithium ion battery as an example, the embodiment provides a ceramic-metal integrated package, which comprises a ceramic body, a molybdenum-manganese layer, a nickel metal layer, a welding material layer and a metal piece which are sequentially connected, wherein
(1) The raw material components used for the molybdenum-manganese layer comprise: the ceramic metal powder comprises the following components in parts by weight: 65 parts of molybdenum powder; 7 parts of manganese powder; 10 parts of porcelain powder; the binder solution comprises a binder and water, wherein the mass ratio of the binder to the water is 1.5:1, and the mass ratio of hydrophilic monomers to hydrophobic monomers in the binder is 1:0.15, wherein the hydrophobic monomer is styrene, the hydrophilic monomer is methacrylic acid, and the styrene and the methacrylic acid are copolymerized in an aqueous phase to prepare the adhesive.
(2) The nickel metal layer comprises the following raw material components: nickel powder and binder solution, wherein the mass ratio of the nickel powder to the binder solution is 0.5:1, wherein the mass ratio of the binder to the water is 1.5:1, and the mass ratio of the hydrophilic monomer to the hydrophobic monomer in the binder is 1:0.15, wherein the hydrophobic monomer is styrene, the hydrophilic monomer is methacrylic acid, and the styrene and the methacrylic acid are copolymerized in an aqueous phase to prepare the adhesive.
(3) The raw material components used for the solder layer comprise: a solder powder and a binder solution, wherein the mass ratio of the solder powder to the binder solution is 0.5:1, a step of; the solder powder comprises a mixture of silver powder, zinc powder and copper powder, wherein the binder solution comprises a binder and water, the mass ratio of the binder to the water is 1.5:1, and the mass ratio of hydrophilic monomers to hydrophobic monomers in the binder is 1:0.15, wherein the hydrophobic monomer is styrene, the hydrophilic monomer is methacrylic acid, and the styrene and the methacrylic acid are copolymerized in an aqueous phase to prepare the adhesive.
Fig. 6 (a) is a full view of a ceramic body of a ceramic seal ring for a power lithium ion battery, fig. 6 (b) is a full view of a ceramic body after molybdenum-manganese metallization, sintered nickel and pre-silver-coated braze in this order, fig. 6 (c) is a front SEM image after pre-silver-coated braze, and fig. 6 (d) is a cross-sectional SEM image after molybdenum-manganese metallization, sintered nickel and pre-silver-coated braze in this order. It can be seen from fig. 6 (b-c) that after the molybdenum-manganese metallization, sintering of nickel and pre-silver coated braze, the entire metal layer remains flat, uniform and free of grooves. It can be seen from fig. 6 (d) that all the metal layers are relatively uniform in thickness, wherein the molybdenum-manganese metal layer has a thickness of about 15 micrometers (the thickness represented by the interval shown by the first white line and the second white line near the alumina substrate in fig. 6 (d)), the nickel metal layer has a thickness of about 10 micrometers (the thickness represented by the interval shown by the second white line and the third white line near the alumina substrate in fig. 6 (d)), and the solder metal layer has a thickness of about 10 micrometers (the thickness represented by the interval shown by the third white line and the fourth white line near the alumina substrate in fig. 6 (d)).
Comparative example 1
The metallization process of the comparative example was the same as that of example 2, except that a 100 micron thick solder piece was used for soldering, and the soldering process parameters were the same as those of example 2. And (3) taking a silver-copper solder sheet with the thickness of 100 microns as solder, placing the solder sheet between a metallized ceramic piece and a metal piece to be soldered, and performing high-temperature soldering at the temperature of about 850 ℃ in vacuum or inert atmosphere or reducing atmosphere to realize packaging.
Fig. 7 is a cross-sectional SEM image of the ceramic seal ring for a power lithium ion battery obtained in comparative example 1 after being welded to a copper metal member. As can be seen from the figure, the thickness of the silver-bronze solder is about 100 μm.
Fig. 8 shows a tensile strength test of a ceramic seal ring for a power lithium ion battery obtained in example 2 by welding with a copper metal member with reference to national industry standard (JC/T2681-2022). In terms of tensile strength, the tensile strength of example 2 and comparative example 1 was about 125mPa, and the tensile strength was not affected by the thickness of the solder metal layer of example 2 reduced to 10 μm.
Example 3
In this embodiment, taking a 5G ceramic transient diode product as an example, a ceramic-metal integrated package is provided, including a ceramic body, a molybdenum-manganese layer, a nickel metal layer, a solder layer, and a metal piece connected in sequence, where
The raw material components used for the molybdenum-manganese layer comprise: the ceramic metal powder comprises the following components in parts by weight: 86 parts of molybdenum powder; 18 parts of manganese powder; 7 parts of porcelain powder; the binder solution comprises a binder and water, wherein the mass ratio of the binder to the water is 0.2:1, and the mass ratio of hydrophilic monomers to hydrophobic monomers in the binder is 1:9, wherein the hydrophobic monomer is isobornyl acrylate, the hydrophilic monomer is 2-acrylamide-2-methylpropanesulfonic acid, and the adhesive is prepared by copolymerizing isobornyl acrylate and 2-acrylamide-2-methylpropanesulfonic acid in an aqueous phase.
(2) The nickel metal layer comprises the following raw material components: the nickel powder and binder solution have a mass ratio of 3:1, wherein the mass ratio of the binder to the water is 0.2:1, and the mass ratio of the hydrophilic monomer to the hydrophobic monomer in the binder is 1:9, wherein the hydrophobic monomer is isobornyl acrylate, the hydrophilic monomer is 2-acrylamide-2-methylpropanesulfonic acid, and the adhesive is prepared by copolymerizing isobornyl acrylate and 2-acrylamide-2-methylpropanesulfonic acid in an aqueous phase.
(3) The raw material components used for the solder layer comprise: the mass ratio of the solder powder to the binder solution is 3:1, a step of; the solder powder comprises the mixture of iron powder, cobalt powder and copper powder, wherein the mass ratio of a binder to water is 0.2:1, and the mass ratio of a hydrophilic monomer to a hydrophobic monomer in the binder is 1:9, wherein the hydrophobic monomer is isobornyl acrylate, the hydrophilic monomer is 2-acrylamide-2-methylpropanesulfonic acid, and the adhesive is prepared by copolymerizing isobornyl acrylate and 2-acrylamide-2-methylpropanesulfonic acid in an aqueous phase.
Fig. 9 (a) is a ceramic body overview of a 5G ceramic transient diode, dimensions of the 5G ceramic transient diode: the diameter is 8mm, the wall thickness is 0.8mm, and the height is 10mm. Fig. 9 (b) is a full view of the solder metal after molybdenum-manganese metallization, nickel sintering, and pre-plating, fig. 9 (c) is a front SEM image of the silver-plated braze after pre-plating, and fig. 9 (d) is a cross-sectional SEM image of the solder after molybdenum-manganese metallization, nickel sintering, and silver-plated braze in that order. It can be seen from fig. 9 (b-c) that after the molybdenum-manganese metallization, sintering of nickel and pre-silver coated braze, the entire metal layer remains flat, uniform and free of grooves. It can be seen from fig. 9 (d) that all the metal layers are relatively uniform in thickness, wherein the molybdenum-manganese metal layer is about 20 micrometers (the thickness represented by the interval shown in fig. 9 (d) near the first white line and the second white line of the alumina substrate), the nickel metal layer is about 8 micrometers (the thickness represented by the interval shown in fig. 9 (d) near the second white line and the third white line of the alumina substrate), and the solder metal layer is about 5 micrometers (the thickness represented by the interval shown in fig. 9 (d) near the third white line and the fourth white line of the alumina substrate).
Comparative example 2
Molybdenum-manganese metallization:
(1) Mixing 70 parts of molybdenum powder, 15 parts of manganese powder and 15 parts of ceramic powder to obtain ceramic metal powder;
(2) Adding 4 parts of ethyl cellulose into 100 parts of terpineol at 60 ℃ and stirring to form a binder solution;
(3) Adding 10 parts of ceramic metal powder and 3 parts of binder solution into a ball milling tank, and stirring and ball milling for 24 hours at 60 ℃ to obtain uniform slurry, wherein the viscosity of the ceramic metal slurry is 5000 mPa.s;
(4) And (3) coating the obtained ceramic metalized slurry on the surface of a ceramic piece in a screen printing mode, wherein a screen is 200 meshes, and then drying and sintering to obtain the metalized ceramic piece.
In the step (2), the drying temperature is 60 ℃ and the drying time is 40 minutes. The sintering temperature in the step (4) is 1500 ℃, and the heat preservation time is 75 minutes.
Electroplating nickel: and (3) putting the molybdenum-manganese-metallized 5G ceramic transient diode into electroplating solution containing nickel ions, reducing and depositing the nickel ions on the surface of the molybdenum-manganese metal at a certain current, filtering, washing and drying to obtain the nickel-metallized ceramic tube.
And (3) welding and packaging: and (3) using a silver-copper solder sheet with the thickness of 0.1mm as a solder, placing the solder between the metallized ceramic piece and the metal piece to be soldered, and performing high-temperature soldering at the temperature of about 850 ℃ in vacuum or inert atmosphere or reducing atmosphere to realize packaging.
Fig. 10 is a cross-sectional SEM image of a 5G ceramic transient diode obtained according to comparative example 2 after being welded with a copper metal piece. As can be seen, the silver-copper solder is not uniform in thickness, and is thicker in the middle, about 100 microns, and thinner on both sides, about 30 microns. This non-uniform thickness results from the grooves created by the molybdenum manganese metallization process.
Fig. 11 is a graph showing the package strength test of a 5G ceramic transient diode obtained in example 2 by welding with a copper metal part and referring to the national industry standard (JC/T2681-2022). In terms of tensile strength, the package strength of example 2 was about 125mPa, and the package strength was not affected by the thickness of the solder metal layer reduced to 5 μm. However, the package strength of comparative example 2 is significantly lower around 105mPa, particularly because: as can be seen from fig. 10, the silver-copper solder has uneven thickness after soldering and packaging, and the intermediate solder has a significantly concave condition, which results in uneven sealing or contact at the intermediate portion, and uneven solder thickness also results in uneven stress, which causes a decrease in packaging strength.
While the present application has been described with reference to a preferred embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the present application, and in particular, the technical features mentioned in the various embodiments may be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (10)
1. A ceramic-metal integrated package is characterized by comprising a ceramic body, a molybdenum-manganese layer, a nickel metal layer, a solder layer and a metal piece which are connected in sequence,
wherein the thickness of the molybdenum-manganese layer is 5-30 micrometers, and the molybdenum-manganese layer comprises the following raw material components: the ceramic metal powder and the binder solution are mixed according to the mass ratio of (0.5-3): 1, wherein the ceramic metal powder comprises the following components in parts by weight: 60-86 parts of molybdenum powder, 7-20 parts of manganese powder and 7-20 parts of porcelain powder;
the thickness of the nickel metal layer is 0.5-15 micrometers, and the nickel metal layer comprises the following raw material components: the nickel powder and the binder solution are in a mass ratio of (1-3): 1, a step of;
the thickness of the solder layer is 3-100 micrometers, and the solder layer comprises the following raw material components: the solder powder and the binder solution, wherein the mass ratio of the solder powder to the binder solution is (0.5-2): 1, a step of; wherein the solder powder comprises at least two of silver powder, zinc powder, copper powder, manganese powder, chromium powder, iron powder, cobalt powder, titanium powder, nickel powder, aluminum powder, molybdenum powder or tin powder;
the binder solution comprises a binder and water, wherein the mass ratio of the binder to the water is (0.2-1.5): 1; the adhesive is a polymer with a hydrophilic monomer and a hydrophobic monomer, and the mass ratio of the hydrophilic monomer to the hydrophobic monomer is 1: (0.15-18);
The structural formula of the hydrophobic monomer is CH 2 ＝CR 1 R 2 Wherein R is 1 is-H or-CH 3 ；R 2 is-CN, -C 6 H 5 、-COOR 3 Wherein R is 3 Is alkyl, cycloalkyl or aryl;
the structural formula of the hydrophilic monomer is as follows: CHR (CHR) 4 ＝CR 5 R 6 Wherein R is 4 And R is 5 Are all-H or-CH 3 or-COOM; r is R 6 is-COOM, -CH 2 COOM、-COO(CH 2 ) 6 SO 3 M、-CONH 2 、-CONHR 7 Wherein R is 7 Is alkyl or cycloalkyl; m is any one of H element or metal element related in ceramic metal powder.
2. The ceramic metal integrated package of claim 1, wherein the composition of the ceramic powder is consistent with or near the composition of the ceramic body.
3. The ceramic-metal integrated package of claim 1, wherein the molybdenum powder and manganese powder in the molybdenum-manganese layer have a particle size of less than or equal to 10 microns.
4. The ceramic-metal integrated package of claim 1, wherein the nickel powder particle size in the nickel metal layer is less than or equal to 5 microns.
5. The ceramic metal integrated package of claim 1, wherein the solder powder particle size in the solder layer is less than or equal to 50 microns.
6. A packaging method of the ceramic-metal integrated package according to any one of claims 1 to 5, comprising the steps of:
(1) Molybdenum-manganese metallization: mixing molybdenum powder, manganese powder and porcelain powder, adding a binder solution, and stirring at 1-90 ℃ to obtain ceramic molybdenum-manganese metallized slurry; coating the obtained ceramic molybdenum-manganese metallized slurry on the surface of a ceramic body, and then drying and sintering to obtain a molybdenum-manganese metallized ceramic piece;
(2) Nickel metallization: stirring and mixing nickel powder and binder solution at 1-90 ℃ to obtain nickel metallization slurry; coating the obtained nickel-metallized slurry on the surface of the molybdenum-manganese metallized ceramic piece, and then drying and sintering to obtain the nickel-metallized ceramic piece;
(3) Pre-coating a solder layer: stirring and mixing the solder powder and the binder solution at the temperature of 1-90 ℃ to obtain solder paste; coating the obtained solder paste on the surface of a nickel-metallized ceramic piece, and then drying and sintering to obtain a ceramic piece pre-coated with a solder layer;
(4) Packaging a metal piece: and welding the metal piece and the ceramic piece with the obtained pre-coated welding layer to obtain the ceramic-metal integrated package piece.
7. The method of claim 6, wherein in step (1) to step (3), the coating method comprises screen printing, spot coating, spray coating, roll coating, dip coating or sputtering.
8. The method of claim 6, wherein the viscosity of the ceramic-molybdenum-manganese-metallized paste in the step (1) is 1500-6000 mPa-s.
9. The method of claim 6, wherein the viscosity of the nickel-metal paste in the step (2) is 2500-4000 mPa-s.
10. The method of claim 6, wherein the viscosity of the solder paste in the step (3) is 3500-6000mpa·s.
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